CN1606494A - Method for making a plastic optical fiber, and resulting plastic optical fiber - Google Patents
Method for making a plastic optical fiber, and resulting plastic optical fiber Download PDFInfo
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- CN1606494A CN1606494A CNA028257782A CN02825778A CN1606494A CN 1606494 A CN1606494 A CN 1606494A CN A028257782 A CNA028257782 A CN A028257782A CN 02825778 A CN02825778 A CN 02825778A CN 1606494 A CN1606494 A CN 1606494A
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
- G02B1/045—Light guides
- G02B1/046—Light guides characterised by the core material
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Abstract
The present invention concerns a method of manufacturing a plastic optical fiber from at least one polymer P, said method being characterized in that said polymer P is a copolymer comprising at least two repeating units P1 and P2 with the following general formulae, i and j corresponding to a repeat number of units: said copolymer P being transparent, amorphous in nature and having a motif P2 content in the range from substantially 30 mole % to 70 mole % when X=F or Cl in P1.
Description
The present invention relates to make the method for plastic optical fiber and the plastic optical fiber that obtains by this method.The present invention relates to step-refraction index plastic optical fiber and graded index plastic optical fiber particularly.
Since they than major diameter, they install simpler than silicon dioxide fibre, be used to comprise that the step-refraction index plastic optical fiber of visible light and far spectral range is favourable.Because they can be applicable to broadband access network, the graded index plastic optical fiber that is used for same spectral range is favourable.The graded index plastic optical fiber comprises at least a base polymer and is called the additional compounds of " adulterant ", and described additional compounds comprises one or more monomers or polymkeric substance.The ratio of base polymer is basic identical in whole fiber, and adulterant from the core of fiber to edge variation, to produce required graded index or step-refraction index.
Because adulterant must exist with the distribution from the core of plastic optical fiber to edge variation, such plastic optical fiber, particularly graded index plastic optical fiber are difficult to make.In fact, fiber must have the index distribution with regular as far as possible mode gradual change, and change of refractive is generally 0.01-0.03 between fibrillar center and edge.
For making such fiber, European patent EP-A-01067222 has described the method for making the gradual change plastic optical fiber, and wherein refractive index changes between the center and peripheral of fiber continuously.
In described method, make fiber from least a polymer P and at least a reactive diluent D1, described thinning agent makes the variations in refractive index of fiber as adulterant.
Described method comprises following steps:
Preparation has two kinds of compositions of different refractivity, and the refractive index difference between two kinds of compositions is at least 5 * 10
-3, comprising polymer P separately at least, a kind of composition that is called first composition also comprises reactive diluent D1 at least, has radical polymerization initiator at least a composition;
Effectively mix (active mixing) two kinds of compositions to obtain the continuous variation of optical fibre refractivity;
With the potpourri spinning;
Curing mixture has the plastic optical fiber of refractive index gradient with manufacturing.
According to described method, selective polymer P and reactive diluent D make:
The molal weight of polymer P is that the molal weight of 1000-20000 gram/mole and reactive diluent D1 is a 100-1000 gram/mole
Reactive diluent D1 comprises at least a reactive unsaturated group of UV that is selected from the group of vinyl and acrylic groups formation.
Above-mentioned molal weight is a mumber average molar mass.All molal weights of below mentioning also are like this.
In above-mentioned document, the base of optimum selection polymkeric substance is poly-(α-fluorine) methyl acrylic ester type and PMMA (polymethylmethacrylate) type more preferably.
Because the height of c h bond absorbs in this polymkeric substance, the application of the fiber that obtains from this polymkeric substance is limited to the visible wavelength less than 800 nanometers (nm).
Therefore, the purpose of this invention is to provide the graded index optical fiber manufacturing method that is used to make plastic optical fiber, described plastic optical fiber can work under the wavelength greater than 500nm and not cause the unallowed decay of transmitting optical signal.
Therefore the present invention proposes a kind ofly to make the method for plastic optical fiber from least a polymer P, and described method is characterised in that described polymer P is to comprise at least two kinds to have the repetitive P1 of following general formula and the multipolymer of P2, and i and j are corresponding to the repeat number of unit:
Described copolymer p is transparent, is unbodied in essence, and the quantity of unit (motif) P2 is 30 moles of %-70 mole % substantially when X=F among the P1 or Cl.
Above-mentioned multipolymer has the desired light and heat mechanical property of the plastic optical fiber of manufacturing, described multipolymer is colourless and transparent, be dissolved in common organic solvent (particularly acetone, THF, ethyl acetate), glass transition temperature is greater than 60 ℃, be used for known method and make plastic optical fiber, particularly the graded index plastic optical fiber is decayed less than the decay of the fiber that obtains from the prior art polymkeric substance.
Method of the present invention can be applicable to make the graded index plastic optical fiber and makes the step-refraction index plastic optical fiber.
Can be from obtaining copolymer p as the chloro trifluoro ethylene of industrial fluorinated monomer or the vinylene carbonate of tetrafluoroethene and the easy non-halogenated monomer that obtains of conduct.
Therefore multipolymer comprises many fluorine, and than the less hydrogen of prior art PMMA type polymer, causes the transparency that increases, and has ring texture, causes impalpable structure and therefore causes improved optical transmission performance.Therefore, the fiber that is obtained by the inventive method is particularly suitable for being longer than 500nm at wavelength, typically uses near the transmission window 650nm, 850nm, 1300nm and 1550nm.
Highly beneficial ground, in the first embodiment, the present invention propose a kind of method with from described at least polymer P and at least a reactive diluent D1 to change the refractive index of optical fiber, make the step-refraction index plastic optical fiber, the refractive index of described optical fiber is discontinuous variation between the center and peripheral of fiber, or make graded index optical fiber, and the refractive index of described optical fiber changes between the center and peripheral of fiber continuously, and described method is characterised in that it comprises the steps:
Preparation has two kinds of compositions of different refractivity, and the refractive index difference between two kinds of compositions is at least 5 * 10
-3, comprising polymer P separately at least, a kind of composition that is called first composition also comprises reactive diluent D1 at least, has radical polymerization initiator at least a described composition;
Spinning;
The curing activity thinning agent is to make plastic optical fiber.
When plastic optical fiber was the graded index fiber, described method comprised also that after the step of making described composition two kinds of compositions of effective mixing are to produce optical fibre refractivity continually varying step, subsequently with described potpourri spinning.
Advantageously, curing is that photocuring and initiating agent are photoinitiators.
Advantageously, the molal weight of polymer P is that the molal weight of 1000-20000 gram/mole and reactive diluent D1 is a 100-1000 gram/mole.These scopes have limited the viscosity of composition and have promoted spinning.
Also advantageously, reactive diluent D1 comprises at least a active unsaturated group of UV that is selected from the group of vinyl and acrylic groups formation.
The mixing that " effectively mixing " in the inventive method is to use utility appliance to carry out, promptly it is not only to form by diffusion; Described effective mixing can staticly produce, and by static diffusion way, usually by forced flow, or by producing the dynamic means of described mixing energetically, comes the Forced Mixing two compositions.Be actually and produce the concentration steepness, this kind method has advantage rapidly, and it is more faster than only use diffusion between composition, so this method has continuously and the advantage of almost level and smooth refractive index.
Usually cure kinetics makes that gel time is less than 10 seconds (s), preferably less than 2s under highest luminance and initiating agent transform fully.
The method according to this invention is carried out the photochemical solidification or the heat curing of thinning agent after the spinning of graded index potpourri, cause the generation of three-dimensional lattice.Advantageously, the component of the partly solidified at least plastic optical fiber of the method.Obtain plastic optical fiber, and its refractive index gradient is therefore stable and to temperature stabilization to the time.Under these circumstances, at least a monomer that comprises of general two kinds of compositions; In addition, at least a at least a radical polymerization initiator, each self-contained at least a radical polymerization initiator of preferred two kinds of compositions of comprising of two kinds of compositions.Radical polymerization initiator is to decompose the compound that produces the initiating agent free radical by heat or photochemistry.
In one embodiment, second composition comprises at least a reactive diluent D2 that makes its variations in refractive index, the refractive index of reactive diluent D2 is different from the refractive index of D1 substantially, have the molal weight of 100-1000 gram/mole, and comprise at least a reactive unsaturated group of UV that is selected from the group of vinyl and acrylic groups formation.
Preferably, reactive diluent D1 and D2 have viscosity much at one, and for every kind of composition, polymer P almost is constant with respect to the part by weight of composition component.Along with the variation of reactive diluent D1 and/or D2 ratio, and this method of easier enforcement, refractive index can be changed and influence the viscosity of composition indistinctively.
According to a kind of embodiment of the inventive method, making that two kinds of compositions are 1 Pascal-second (Pa.s)～25Pa.s when viscosity is at 20 ℃ separately, be preferably under the temperature of 1Pa.s～15Pa.s, mix two kinds of compositions.Because described viscosity can make the composition of phase liquid towards mix, this advantageously promotes the enforcement of the inventive method.
According to a kind of embodiment of the inventive method, make two kinds of compositions separately viscosity be preferably greater than under the temperature of 1000mPa.s and carry out spinning for greater than 500mPa.s.
The reactive group that is carried by component D1 and D2 is selected from the group that vinyl and acrylic groups form, and promptly is selected from acrylate, methacrylate, vinyl ether and propenyl ether; Described compound can be partially halogenated at least, fluoridize usually and/or chlorination.
In an embodiment of the inventive method, every kind of component of one of composition is partially halogenated at least material, fluoridize usually and/or chlorination.
Variant according to the inventive method, when wherein in second composition, existing under the situation of reactive diluent D2, a kind of D1 of two kinds of reactive diluents or D2 are partially fluorinated at least, with the another kind of D2 of two kinds of reactive diluents or D1 be to the small part chlorination or chlorofluorination, so refractive index is higher than the refractive index of at least a partially fluorinated monomer substantially.
In second embodiment, the present invention propose a kind of from described at least polymer P and at least a adulterant D to change the refractive index of described optical fiber, make the method for graded index optical fiber, the refractive index of described optical fiber changes between the center and peripheral of fiber continuously, the refractive index of described adulterant D is higher than the refractive index of described polymer P, and described method comprises the steps:
Molten polymer P in pipe;
Make of the axle rotation of described pipe around it;
Cool off described pipe to form the tubular body of polymer P at described tube interior;
In the tubular body that forms by polymer P, introduce described adulterant D;
Heating also makes the axle rotation of described pipe around it, with by the described adulterant D of described polymer P thermal diffusion, and the tubular body of formation doped polymer P;
Cooling is to obtain the tubulose prefabrication;
Stretching is connected to the described tubulose prefabrication of vacuum pump to form plastic optical fiber.
In the 3rd embodiment, the present invention proposes a kind of method of making the step-refraction index plastic optical fiber from described at least polymer P, the refractive index of described optical fiber is discontinuous variation between the center and peripheral of fiber, the spinning under molten state of described polymer P, and apply with light-cured resin simultaneously, the refractive index of described light-cured resin is lower than the refractive index of polymer P, then the described light-cured resin of photopolymerization.
At last, in the 4th embodiment, the present invention proposes a kind of by described polymer P of coextrusion and other polymkeric substance, make the method for step index optical fiber from described at least polymer P, the refractive index of described optical fiber is discontinuous variation between the center and peripheral of fiber, and the refractive index of described other polymkeric substance is lower than the refractive index of described polymer P.
Clearly, also can implement method of the present invention to make optical waveguide.
The present invention also provides graded index plastic optical fiber that is obtained by the inventive method and the optical waveguide that is obtained by the inventive method.
By the description to the embodiment that provides in the mode of non-limiting example of the present invention, other features and advantages of the present invention will become clearly.
In as figure below:
Fig. 1 illustrates the equipment that is used to implement the inventive method;
Fig. 2 illustrates the index distribution of the optical fiber that uses the acquisition of Fig. 1 equipment;
Fig. 3 shows the decay spectrum of the plastic optical fiber that obtains from art methods with according to the method for one embodiment of the present invention.
In all figure, common element has identical label.
In the method for the invention, prepare two kinds of compositions, each self-contained copolymer p.One of described composition also comprises at least a reactive diluent D1, and it is preferably monomer.Randomly, another composition comprises at least a reactive diluent D2, and it is monomer preferably also.The concentration of D1 is different in each of two kinds of polymkeric substance, and this causes every kind of composition that different refractive indexes is arranged.Two numerical value of the refractive index that obtains constitute maximal value and the minimum value on the refractive index gradient parabolic line chart, obtain described parabolic line chart and are used for from the plastic optical fiber (referring to Fig. 2) of this method acquisition.
The copolymer p that is used for the inventive method promptly, comprises repetitive P1 and P2 shown below as defined above:
Unit P1 derived from a polymerization i monomer M 1 and unit P2 derived from a polymerization j monomer M 2.
Monomer M 1 is the fluorinated monomer of being represented by following general formula: CF
2=CFX, wherein X be following any:
Fluorine atom, M1 is a tetrafluoroethene under described situation;
The chlorine atom, M1 is a chloro trifluoro ethylene under described situation.
Repetitive P1 can be derived from the potpourri of the monomer with formula M 1.
The comonomer M2 that generates repetitive P2 is the vinylene carbonate with following structural formula:
Can adopt any known polymerization methods of making polymer P: for example solvent polymeric (solventpolymerization), the suspension polymerization in water or emulsion polymerization.Generally speaking, preferably in solvent, operate with the exothermic nature of controlling polymerization and the abundant mixing that promotes different monomers.
The example of adducible normally used solvent is: ethyl acetate, methyl acetate or butyl acetate and chlorination or chlorofluorination solvent such as F141b (CFCl
2-CH
3) or F113 (CF
2Cl-CFCl
2).
The radical polymerization initiator that uses can be free-radical generating agent such as superoxide, hydroperoxides or percarbonate, or diazo-compounds such as azoisobutyronitrile (AIBN).When in water-bearing media, implementing this method, can use inorganic free-radical generating agent such as persulfate or redox bond (radoxcombination).
Polymerization temperature is generally determined by the decomposition rate of selected initiating agent, and is generally 0 ℃-200 ℃, more specifically 40 ℃-120 ℃.
Pressure is generally the pressure that atmosphere is pressed onto 50 crust, more specifically 2 crust-20 crust.
In order to provide polymer P is formed better control, also can be in polymerization process, continuously or the piecewise introduce all or part of monomer and initiating agent.
The glass transition temperature (Tg) that is used for the copolymer p of the inventive method is 60 ℃-160 ℃, preferred 80 ℃-140 ℃.This glass transition temperature is mainly relevant with the quantity of unit (motif) P2 that exists in the multipolymer.The transparency of the polymkeric substance that obtains also depends on the quantity of unit P2.
Derived from the repetitive of polymerization single polymerization monomer M2, the quantity of unit P2 can be in multipolymer as the function of X essence among the P1 and change.When X=F or Cl, the quantity of unit P2 is 30 moles of %-70 mole % substantially in the multipolymer in P1.
Not to prejudice of the present invention, also can between polymerization period, introduce the 3rd monomer, condition be in the multipolymer that forms its quantity less than 15 moles of %.
The molal weight of the polymer P of the inventive method (Mn) is 500-10
6Gram/mole, preferred 10
3-10
4Gram/mole.
Now in the embodiment of following preparation copolymer p, the present invention is made an explanation.
The reactant that uses, initiating agent and solvent have following abbreviation:
CTFE: chloro trifluoro ethylene CF
2=CFCl
TFE: tetrafluoroethene CF
2=CF
2
VCA: vinylene carbonate
TBPP: cross the neopentanoic acid tert-butyl ester, 75% weight in Permethyl 99A
F141b : 1,1, the 1-chloro fluoroethane
Mn value (mumber average molar mass) is definite by SEC (spatial exclusion chromatography).Use is from " Winner Station " instrument of Spectra Physics.Detect with refractive index.The chromatographic column of using is the C PL gel column of 5 microns mixing, and from Polymer Laboratories, and the solvent that uses is THF, flow velocity 0.8ml/min.Mumber average molar mass (Mn) is with respect to polystyrene standards, represents with gram/mole.
Measure Tg (glass transition temperature) by differential scanning calorimetry (DSC).Initially with 20 ℃/min rising cooling subsequently, the temperature that raises for the second time then reads Tg or Tf (melt temperature) during this period with temperature.If Tg is higher than 60 ℃, temperature range is 50 ℃-200 ℃.
Usually in the PARR bullet by Na
2O
2Mineralising by argentometry method analyzing chloride, is determined chlorinity then.
Embodiment 1
[M1/M2：CTFE/VCA]
Use 160 milliliters of (ml) stainless steel reactors, under 5 crust nitrogen, purify twice or three times.By sucking, the 50ml F141b solution that will comprise 0.6ml TBPP initiating agent (2.25 mM) and 8.53g VCA (99 mM) is introduced the reactor (about 100 millibars of pressure) of emptying then.Introduce 11gCTFE (94.5 mM) then.Under the original pressures of stirring and about 10 crust, reaction medium is heated to 80 ℃, and kept 2 hours (h) 30 minutes.After reaction, the content of autoclave is partly evaporated, adopt heptane to precipitate vacuum drying then.
Acquisition is dissolved in usual solvents (acetone, 16.2g multipolymer THF).Analysis that the multipolymer that obtains among the embodiment 1 is carried out shows that the P1/P2 ratio is 47/53, the Tg of the Mn of 7400 gram/moles and 120 ℃.Obtain the clear, colorless film when in ethyl acetate, dissolving and evaporating.
Embodiment 2
[M1/M2：CTFE/VCA]
Follow the process of embodiment 1, use identical reagent and identical ratio, use ethyl acetate to replace F141b as solvent.When reaction finishes, obtain the polymer solution in the ethyl acetate.Evaporating solvent uses normal heptane precipitation reaction product then to obtain the volume of about 20ml.With the polymer filtration of precipitation, then 60 ℃ of following vacuum drying.It is transparent to obtain 10g, colourless multipolymer, and described multipolymer dissolves in THF or acetone.Mol ratio P1/P2 be 49/51 and Tg be 106 ℃.
This multipolymer of 1g taken out and be dissolved in 3ml ethyl acetate.The solution that obtains is fully limpid.In 7 centimetres of (cm) flat crystallizers this solution of deposition and under environment temperature and atmospheric pressure evaporating solvent 3 days.The film that obtains is fully transparent and limpid.
Embodiment 3-7
For comparative example 3,5,6 and 7 and embodiment 4, follow the process of embodiment 2, use reactant CTFE and the VCA quantity shown in the following table 1.
Comparative example shown in the table 1 uses x mM CTFE and y mM VCA, and x and y have following value:
Embodiment 1:x=94.5 and y=99;
Embodiment 2:x=95 and y=98;
Comparative example 3:x=186 and y=40;
Embodiment 4:x=86 and y=174;
Comparative example 5:x=181 and y=10.5;
Comparative example 6:x=43 and y=174;
Comparative example 7:x=0 and y=180.
Be displayed in Table 1 the mol ratio P1/P2 of embodiment 1-7, as the polymer yield of mole % acquisition, from M1 and the polymer solution outward appearance of M2 polyreaction acquisition and the outward appearance of described polymer film.
Table 1
| Embodiment | Molar percentage P1/P2 (1) | Yield (%) | Solution appearance (2) | Observation to the film that obtains |
| 1 | ??47/53 | ????# | Limpid | Transparent Tg120 ℃ |
| 2 | ??49/51 | ????51％ | Limpid | Transparent Tg106 ℃ |
| 3 | ??85/15 | ????28％ | Limpid | Transparent Tg＜50 ℃ |
| 4 | ??33/67 | ????49％ | Limpid | Transparent |
| 5 | ??95/5 | ????5％ | Limpid | Milky |
| 6 | ??20/80 | ????60％ | There are many insolubless | Transparent+opaque insolubles |
| 7 | ??0/100 | ????70％ | There is insolubles | Opaque insolubles |
(1) has the P1 of CTFE comonomer M1 and have the P2 of VCA comonomer M2
(2) solution: the 1g polymkeric substance in 3ml ethyl acetate.
As can be seen for comprising the embodiment 1,2 and 4 that molar ratio P1/P2 is 70/30-30/70 and M1=CTFE and M2=VCA substantially, the solution of the copolymer p of acquisition is limpid and is transparent solid at the co-polymer membrane that obtains after described solution evaporation solvent.Be positioned under the above comparative example 3,5,6 and 7 situation who quotes beyond the scope at mol ratio P1/P2 as can be seen, the film of multipolymer is non-transparent solid.
Embodiment 8
[M1/M2：TFE/VCA]
Follow the process of embodiment 2, but use 7g (81.3 mM) VCA and 11g (110 mM) TFE replaced C TFE.Obtain 14.6 multipolymers.The multipolymer height is dissolved in acetone or THF.When evaporation acetone, obtain the clear, colorless film.
19F NMR analyzes and shows 70/30 mol ratio P1/P2.The Tg of multipolymer is 82 ℃ (dsc analysis).
Also adopt M1=TFE and M2=VCA to carry out other test.Demonstration obtains the co-polymer membrane of substantially transparent for being the mol ratio P1/P2 of 70/30-30/70 substantially.
For example use an above-mentioned embodiment,, prepare two kinds of composition C1 and C2, to make optical fiber by the UV type method according to the present invention in case obtain copolymer p.
Make two kinds of different compositions, the reactive diluent that it comprises the active copolymer P of commercially available light trigger, the foregoing description 1,2 or 3 and contains two kinds of monomers, depend on composition, the ratio difference of two kinds of monomers, described two kinds of monomers are (D1) and (D2).
Photoinitiator can be, for example, and alpha-alcohol ketone (IRGACURE 184, and DAROCUR 1173), monoacyl phosphine (DAROCUR TPO) or two acylphosphanes (IRGACLURE 819).
D1 and D2 have at least one acrylic acid, methacrylic acid, α-perfluoroalkyl acrylate, a α, β-two perfluoroalkyl acrylate or contain the monomer of the vinyl-functional of halogenation group (fluoridizing or chlorination).
Following table 2 shows composition and the character of composition C1 and C2, and described composition is that active terpolymer P, reactive diluent D1 acrylic acid trifluoroethyl ester (refractive index at 20 ℃ of its homopolymer is 1.407) and the reactive diluent D2 methacrylic acid trifluoroethyl ester (refractive index at 20 ℃ of its homopolymer is 1.437) by mix embodiment 7 prepares.Light trigger is from two-acylphosphanes class (BAPO-IRGACURE 819).This tittle is to calculate with respect to 700 compositions that restrain.
Table 2
| Composition | The quality of D1 (g) | The quality quantity (g) of D2 | The quality quantity (g) of P |
| ????C1 | ??35 | 315 | 350 |
| ????C2 | ??140 | 210 | 350 |
As can be seen, the copolymer p of every kind of composition is constant to the weight % of each component summation, and in reactive diluent, D1 is to the weight % of D1 and D2 summation, and promptly relative scale is different in two kinds of compositions.This allows to control the viscosity of two kinds of compositions by changing the refractive index of every kind of described composition.
The method according to this invention for preparation graded index fiber, by two kinds of starting composition C1 of effective mixing and C2, has formed continuous variations in refractive index.For this purpose, use blend tool to realize method of the present invention, this instrument can be static or dynamic mixer.Obtained detailed description among this EP-A-1067222 of being implemented in, be introduced into as a reference.The details that is used for the function of the static state of the inventive method or dynamic mixer here no longer provides, and method of the present invention is described will be enough simply, described method is to use one of static mixer described in the EP-A-1 067222 to implement.
Fig. 1 is the method according to this invention, is used to make the cross sectional representation that the height of devices of optical fiber is summarized, and this xsect is along the plane of the central shaft X that comprises this device.
Equipment 10 comprises static mixer 1.Mix composition C1 and the C2 that goes up table therein.
Mixer 1 comprises as two concentric circles cylindrical shells 3 of composition C1 and C2 reservoir and 4.The cylindrical chamber 8 of mixer 1 is as the reservoir 4 of composition C2.In the reservoir of center, place and have the more composition C1 of high index of refraction.
Chamber 8 comprises top anti-leak closure member 8d, and described closure member comprises two inlet 8g and 8f separately, and described inlet is separately producing controlled pressure in the reservoir 3 and 4 separately, for example uses two volumetric pump (not shown)s.Therefore, if two kinds of composition C1 have identical viscosity with C2, controlled pressure can be applied to two kinds of composition C1 and C2 to obtain identical flowing.But also possible, opening 8f and 8g are applied different controllable pressures, for example have under the different viscosity situations at two kinds of composition C1 and C2, wish that every kind of composition C1 or C2 have different flow velocitys.Chamber 8 comprises also that wherein two reservoirs 3 and 4 are that regional 8e and its upper limit concentric and separated from one another is that center reservoir 3 bottoms and its lower limit are the regional 8a of outside reservoir 4 bottoms.Zone 8a is corresponding to the mixed zone that is used for two kinds of composition C1 and C2 by mixer 1, promptly by superimposed plates (2a, the assembly 2 2b) of hole twelve punch.Chamber 8 also comprises and the xsect position wherein occurs like the tapered zone 8b that changes (homothetic variation), finally comprise steepness district (graded zone) 8c of die head 15, described steepness district 8c provides the required order of magnitude of graded index plastic optical fiber 6 diameters of acquisition.Die head 15 is web members, and the gradient that this means it can easily change and need not to change mixer 1.
The regional 8a of mixer 1 comprise be superimposed upon over each other at least two and in the case seven perforated plates (2a, 2b).(2a, assembly 2 2b) is to guarantee the radially mixing of composition C1 and C2 at the lower end of center reservoir 3 placing plate.Obtain potpourri 5 in regional 8a, it has the concentration gradient of composition C1 and C2.Because (2a, stack 2b) forms potpourri 5 to plate.Each plate 2a (or 2b) comprises hole 12, and (or from a plate 2b to adjacent panels 2a) reciprocally arranges described hole generally from a plate 2a to adjacent panels 2b.A common plate 2a and the plate 2b that closes on (or a plate 2b with the plate 2a that closes on) are disposed opposite to each other.Under situation shown in Fig. 1, two class plates are arranged, plate 2a, 4; Plate 2b, 3, each plate 2a or 2b comprise about same number of hole 12.
By tapered zone 8b the potpourri 5 that obtains is delivered to the steepness die head 15 of the regional 8c of chamber 8, the upper limit of described tapered zone 8b is the lower end of last plate 2a.This is like changing the shape that has kept composition C1 and C2 concentration change.
In the outlet of die head 15, obtain long filament (filament) by capstan winch 10 stretchings, it is a graded index plastic optical fiber 6.In one embodiment, use UV radiation (UV) source 7 plastic optical fiber 6 to be solidified into the plastic optical fiber 9 of polymerization by photocuring.Use capstan winch that plastic optical fiber 9 is wound up on the spool 11 then.The diameter of fiber 9 is provided by die head 15, but depends on the tensile force that is produced by capstan winch 10, and it can become thinner.Plastic optical fiber 6 or 9 can be used and finished product of the present invention.
Fig. 2 shows the index distribution of the optical fiber that uses Fig. 1 device fabrication.Provide the index distribution n of Fig. 1 optical fiber 6, it makes smoothly that almost its formation is shaped as parabolical gradient, is the function apart from r at distance fiber 6 centers, and described center is on axle X.
Therefore the fiber that obtains is the graded index fiber, but above method also allows to obtain step index fiber.Under described situation, do not carry out effective mixing of composition C1 and C2.C1 and C2 are introduced the distributor jar (distributor can) that is extended by die head, wherein by the final diameter of the pressure and temperature of composition C1 and C2 and die diameter controlling fiber and core ratio to coating (cladding).
The present invention also relates to make the method for other type of plastic optical fiber.
Be to make the graded index plastic optical fiber, can use the method among the US-A-6071441 of being described in that is called the prefabrication method.
In an example of embodiment, for making prefabrication, under 200-250 ℃ temperature in cylindrical glass tube fusion 100g CTFE/VCA copolymer type polymer P, wherein the molar ratio of CTFE unit is 30%-70%, and the quality average molar mass of polymer P (mass average molarmass) is about 5 * 10
5, and not exclusively fill described glass tube, and made before the vacuum lower seal, in comprising the pipe of polymer P, produce void space.In baking oven, glass tube is placed on horizontal level then.Then with it around its horizontal rotational shaft (speed is fixed on 2000 rev/mins), and making that the viscosity of molten polymer P is 10
3-10
5Under the temperature of pool, heated oven three hours.In one hour, slowly cool off pipe then.The external diameter of the tubular body that obtains is that 17mm and internal diameter are 5mm, and its refractive index is 1.45.
Then adulterant D is introduced the core of described tubular body, described tubular body is still in glass tube.Its ratio with respect to polymer P is 4% weight.Be the material that makes that adulterant is suitable for using, preferably it satisfies following two conditions:
Its refractive index n is higher than the refractive index of polymer P;
The solubility parameters difference of polymer P and adulterant D, | δ p-δ
D| be 7 or littler (cal/cm
3)
1/2
Following table 3 has been summed up several examples of the compound of the adulterant D that can be used as this application.
Table 3
| Adulterant D | ????n | ????δ(cal/cm 3) 1/2 |
| Normal-butyl benzyl phthalic ester | ????1.575 | ????9.64 |
| 1-aminomethyl phenyl-1-diphenylphosphino ethane | ????1.571 | ????9.74 |
| Ergol | ????1.568 | ????10.7 |
| Bromobenzene | ????1.557 | ????9.9 |
| O-dichlorobenzene | ????1.551 | ????10.0 |
| M-dichlorobenzene | ????1.543 | ????9.9 |
| 1, the 2-ethylene dibromide | ????1.538 | ????10.4 |
| 3-phenyl-1-propyl alcohol | ????1.532 | ????11.4 |
Rotary integral once more in baking oven.Adulterant D passed through molten polymer P thermal diffusion in 6 hours.At last, 15 ℃/hour speed baking oven slowly is cooled to environment temperature.Acquisition has refractive index gradient, and external diameter is that 17mm and internal diameter are the tubular body of 4.5mm.
Under 200-250 ℃ temperature, this tubular body that constitutes the plastic optical fiber prefabricated product of graded index is placed in the baking oven.Top with it during the spinning step is connected to vacuum pump.In this way, prefabrication shrinks, and reclaims the optical fiber with refractive index gradient.Its size depends on spinning speed, and this speed is preferably 5-10m/min, and depends on oven temperature.
Advantageously, use glass transition temperature to be higher than PMMA or those polymer Ps of CYTOP, PMMA or CYTOP are the materials that is generally used for known " prefabrication " method, produce the transparency and are higher than those the fiber that is obtained by conventional material.This illustrates in Fig. 3, Fig. 3 shows the function of conduct with the wavelength of nm, use the damping capacity (in dB/km) of said method: prior art polymkeric substance CYTOP (curve 31), prior art polymer P MMA (curve 32) and (CTFE) 0.50 of the present invention (VCA) 0.50 (curve 33) from the graded index plastic optical fiber of following material acquisition.
For making step-refraction index plastic optical fiber of the present invention, for example can and deposit the light-cured resin that refractive index is lower than refractive index polymer simultaneously in spinning under the molten state, then the described resin of photopolymerization at the polymer P of making described in the above embodiment of the present invention.For example, the resin layer thickness of deposition is the order of magnitude of 100 μ m.
Alternatively, for making step-refraction index plastic optical fiber of the present invention, can the coextrusion polymer P and refractive index be lower than the polymkeric substance of polymer P and carry out, as PVDF, available from the Teflon AF of Pont de Nemours or available from the Hyflon AD of AUSIMONT.
Two kinds of methods itself mentioning at last are that those of skill in the art are known, do not further describe at this.
Clearly, method of the present invention is not limited to above-described embodiment.
Can use any equipment that is suitable for producing effective mixing as the equipment of making graded index optical fiber, particularly but not exclusively be described in the equipment of EP-A-1067222.
In addition, above-mentioned composition and embodiment only provide as an illustration, and scope of the present invention comprises they are improved, and condition is that copolymer p keeps the above-mentioned general character.
At last, scope of the present invention comprises by any equal measure and replaces any measure.
Claims (21)
1. make the method for plastic optical fiber from least a polymer P for one kind, described method is characterised in that described polymer P is to comprise at least two kinds to have the repetitive P1 of following general formula and the multipolymer of P2, and i and j are corresponding to the repeat number of unit:
Described copolymer p is transparent, is unbodied in essence, and when X=F among the P1 or Cl, the quantity of unit P2 is 30 moles of %-70 mole % substantially.
2. according to the method for claim 1, be used for from described at least polymer P and at least a reactive diluent D1 to change the refractive index of optical fiber, make the step-refraction index plastic optical fiber, the refractive index of described step index optical fiber is discontinuous variation between the center and peripheral of fiber, or graded index optical fiber, the refractive index of described graded index optical fiber changes between the center and peripheral of fiber continuously, and described method is characterised in that and comprises the steps:
Preparation has two kinds of compositions of different refractivity, and the refractive index difference between described two kinds of compositions is at least 5 * 10
-3, comprising polymer P separately at least, a kind of composition that is called first composition also comprises reactive diluent D1 at least, has radical polymerization initiator at least a described composition;
Spinning;
Solidify described reactive diluent to make plastic optical fiber.
3. according to the method for claim 2, it is characterized in that when described plastic optical fiber is the graded index fiber, described method comprises also that after the step of making described composition the described two kinds of compositions of effective mixing are to produce optical fibre refractivity continually varying step, subsequently with described potpourri spinning.
4. according to the method for claim 2 or 3, it is characterized in that described curing is photocuring, and described initiating agent is a photoinitiator.
5. according to each method among the claim 2-4, the molal weight that it is characterized in that described polymer P is that the molal weight of 1000-20000 gram/mole and described reactive diluent D1 is a 100-1000 gram/mole.
6. according to each method among the claim 2-5, it is characterized in that described reactive diluent D1 comprises at least a active unsaturated group of UV that is selected from the group that vinyl and acrylic groups form.
7. according to each method among the claim 2-6, the glass transition temperature that it is characterized in that described multipolymer is 60-160 ℃.
8. according to each method among the claim 2-7, the molal weight that it is characterized in that described multipolymer is 500-10
6Gram/mole.
9. according to each method among the claim 2-8, it is characterized in that cure kinetics makes that gel time was less than 10 seconds under highest luminance and initiating agent transform fully.
10. according to the method for claim 9, it is characterized in that described gel time was less than 2 seconds.
11. according to each method among the claim 2-10, second kind that it is characterized in that described composition comprises at least a reactive diluent D2 that makes its variations in refractive index, the refractive index of described reactive diluent D2 is different from the refractive index of D1 substantially, have the molal weight of 100-1000 gram/mole, and comprise at least a active unsaturated group of UV that is selected from the group of vinyl and acrylic groups formation.
12. according to the method for claim 11, the viscosity that it is characterized in that described reactive diluent D1 and D2 much at one, and for every kind of described composition, described polymer P is almost constant with respect to the weight ratio of composition component.
13., it is characterized in that making that every kind of described composition is to mix two kinds of compositions under the temperature of 1-25Pa.s in the viscosity under 20 ℃ according to each method among the claim 3-12.
14., it is characterized in that making the viscosity of every kind of two kinds of composition under greater than the temperature of 500mPa.s, carry out spinning according to each method among the claim 2-13.
15. according to each method among the claim 2-14, the every kind of component that it is characterized in that one of described composition is partially halogenated at least material.
16. method according to claim 15, it is characterized in that when having reactive diluent D2 in second kind at described composition, a kind of D1 of two kinds of reactive diluents or D2 be partially fluorinated at least, and the another kind of D2 of two kinds of reactive diluents or D1 be to the small part chlorination or chlorofluorination.
17. method according to claim 1, be used for from described at least polymer P and at least a adulterant D to change the refractive index of optical fiber, make the graded index plastic optical fiber, the refractive index of described optical fiber changes between the center and peripheral of fiber continuously, the refractive index of described adulterant D is higher than the refractive index of described polymer P, and described method comprises the steps:
Molten polymer P in pipe;
Make of the axle rotation of described pipe around it;
Cool off described pipe to form the tubular body of described polymer P at described tube interior;
In the described tubular body that forms by polymer P, introduce described adulterant D;
Heating and make the axle rotation of described pipe around it with by the described adulterant D of described polymer P thermal diffusion, and forms the tubular body of the polymer P of doping;
Cooling is to obtain the tubulose prefabrication;
Stretching is connected to the described tubulose prefabrication of vacuum pump to form plastic optical fiber.
18. method according to claim 1, be used for making the step-refraction index plastic optical fiber from described at least polymer P, the refractive index of described optical fiber is discontinuous variation between the center and peripheral of fiber, the spinning under molten state of described polymer P, and apply with light-cured resin simultaneously, the refractive index of described light-cured resin is lower than the refractive index of polymer P, then the described light-cured resin of photopolymerization.
19. method according to claim 1, be used for by described polymer P of coextrusion and other polymkeric substance, make step index optical fiber from described at least polymer P, the refractive index of described optical fiber is discontinuous variation between the center and peripheral of fiber, and the refractive index of described other polymkeric substance is lower than the refractive index of described polymer P.
20. step or graded index plastic optical fiber is characterized in that described optical fiber is by obtaining according to each method among the claim 1-19.
21. an optical waveguide is characterized in that described optical waveguide is by obtaining according to each method among the claim 1-20.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR01/15038 | 2001-11-19 | ||
| FR0115038A FR2832514B1 (en) | 2001-11-19 | 2001-11-19 | METHOD FOR MANUFACTURING AN INDEX GRADIENT PLASTIC OPTICAL FIBER AND INDEX GRADIENT OPTICAL FIBER OBTAINED BY THIS PROCESS |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1606494A true CN1606494A (en) | 2005-04-13 |
Family
ID=8869616
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA028257782A Pending CN1606494A (en) | 2001-11-19 | 2002-11-18 | Method for making a plastic optical fiber, and resulting plastic optical fiber |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US20050062180A1 (en) |
| EP (1) | EP1451005A2 (en) |
| JP (1) | JP2005509912A (en) |
| KR (1) | KR20040066812A (en) |
| CN (1) | CN1606494A (en) |
| FR (1) | FR2832514B1 (en) |
| WO (1) | WO2003043805A2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109540847A (en) * | 2018-12-13 | 2019-03-29 | 山东师范大学 | A kind of graphene/gold/D plastic optical fiber SPR sensor and preparation method |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2832515B1 (en) * | 2001-11-19 | 2004-01-30 | Nexans | METHOD FOR MANUFACTURING AN INDEX GRADIENT PLASTIC OPTICAL FIBER AND INDEX GRADIENT OPTICAL FIBER OBTAINED BY THIS PROCESS |
| US20050157999A1 (en) * | 2002-12-27 | 2005-07-21 | Zhen Zhen | Graded index polymer optical fiber and a method of making the same |
| WO2024011245A2 (en) * | 2022-07-08 | 2024-01-11 | Samtec, Inc. | Additive manufactured waveguide |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4138194A (en) * | 1977-10-14 | 1979-02-06 | E. I. Du Pont De Nemours And Company | Low attenuation optical fiber of deuterated polymer |
| JP2762417B2 (en) * | 1988-04-15 | 1998-06-04 | 三菱レイヨン株式会社 | Manufacturing method of optical transmission body |
| JP2762416B2 (en) * | 1988-04-15 | 1998-06-04 | 三菱レイヨン株式会社 | Manufacturing method of optical transmission body |
| US5760139A (en) * | 1994-04-18 | 1998-06-02 | Yasuhiro Koike | Graded-refractive-index optical plastic material and method for its production |
| ES2191050T3 (en) * | 1994-04-18 | 2003-09-01 | Yasuhiro Koike | RESIN OF OPTICAL USE OF THE TYPE OF DISTRIBUTION OF REFRACTION INDEX AND THE PROCEDURE OF PRODUCTION OF THIS RESIN. |
| US5670590A (en) * | 1994-05-06 | 1997-09-23 | Minnesota Mining And Manufacturing Company | Energy polymerizable compositions, homopolymers and copolymers of oxazolines |
| JP3951404B2 (en) * | 1998-01-26 | 2007-08-01 | 旭硝子株式会社 | Electric double layer capacitor |
| FR2784196B1 (en) * | 1998-10-01 | 2000-12-15 | Cit Alcatel | INDEX GRADIENT PLASTIC OPTICAL FIBER AND CONTINUOUSLY MANUFACTURING INDEX GRADIENT PLASTIC OPTICAL FIBER |
| FR2795997B1 (en) * | 1999-07-05 | 2001-10-19 | Cit Alcatel | METHOD FOR MANUFACTURING AN INDEX GRADIENT PLASTIC OPTICAL FIBER |
| FR2832515B1 (en) * | 2001-11-19 | 2004-01-30 | Nexans | METHOD FOR MANUFACTURING AN INDEX GRADIENT PLASTIC OPTICAL FIBER AND INDEX GRADIENT OPTICAL FIBER OBTAINED BY THIS PROCESS |
-
2001
- 2001-11-19 FR FR0115038A patent/FR2832514B1/en not_active Expired - Fee Related
-
2002
- 2002-11-18 EP EP02803435A patent/EP1451005A2/en not_active Withdrawn
- 2002-11-18 JP JP2003545464A patent/JP2005509912A/en not_active Withdrawn
- 2002-11-18 WO PCT/FR2002/003932 patent/WO2003043805A2/en not_active Application Discontinuation
- 2002-11-18 CN CNA028257782A patent/CN1606494A/en active Pending
- 2002-11-18 KR KR10-2004-7007348A patent/KR20040066812A/en not_active Application Discontinuation
- 2002-11-18 US US10/496,100 patent/US20050062180A1/en not_active Abandoned
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109540847A (en) * | 2018-12-13 | 2019-03-29 | 山东师范大学 | A kind of graphene/gold/D plastic optical fiber SPR sensor and preparation method |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20040066812A (en) | 2004-07-27 |
| FR2832514B1 (en) | 2004-01-30 |
| US20050062180A1 (en) | 2005-03-24 |
| WO2003043805A2 (en) | 2003-05-30 |
| FR2832514A1 (en) | 2003-05-23 |
| WO2003043805A3 (en) | 2003-12-11 |
| EP1451005A2 (en) | 2004-09-01 |
| JP2005509912A (en) | 2005-04-14 |
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